Formulations comprising water-soluble granulates

ABSTRACT

The present invention relates to formulations comprising water-soluble granulates of phthalocyanine compounds, to a process for the preparation thereof, and to the use thereof in washing agent and washing agent additive formulations.

The present invention relates to formulations comprising water-solublenon-encapsulated granulates of phthalocyanine compounds, to a processfor the preparation thereof, and to the use thereof in washing agent andwashing agent additive formulations.

The formulations according to the invention may be liquid, solid,paste-like or gel-like.

The formulations, especially washing agent compositions but also washingagent additives or additive concentrates, for example pre- and/orafter-treatment agents, stain-removing salt, washing-power enhancers,fabric conditioners, bleaching agents, UV-protection enhancers etc., maybe in any known and customary form, especially in the form of powders,(super-)compact powders, in the form of single- or multi-layer tablets(tabs), bars, blocks, sheets or pastes, or in the form of pastes, gelsor liquids used in capsules or in pouches (sachets).

It is also possible for powders to be used in suitable sachets orpouches.

Water-soluble phthalocyanine compounds, especially zinc and aluminiumphthalocyanine-sulfonates, are frequently used as photoactivators inwashing agent preparations.

EP 333 270 describes solid microcapsules of phthalocyaninephotoactivators, which comprise at least 38% of an encapsulatingmaterial.

EP 959 123 describes granulates based on anionic dispersing agents inconjunction with a water-soluble organic polymer.

EP 323 407 describes encapsulated granules comprising an activeingredient.

EP 124 478 describes a process for the preparation of solidphotoactivator preparations, which comprises passing a crude solution ofthe photoactivators through a modified membrane and subjecting theresulting concentrated aqueous solution to a gentle drying process.

EP 236 270 describes a process for the preparation of structurescomprising an active substance and their use as speckles, having anaverage diameter of 0.5-1.0 mm.

However, owing to the fact that such photoactivators dissolve too slowlyin water, problems often arise, especially when there is inadequatemixing of the washing liquor, because the coloured photoactivators stainthe laundry.

It has now been found that the rate at which granules of phthalocyaninecompounds dissolve in water can be improved further by a novelcomposition. This is achieved by the addition of at least one inorganicsalt and/or at least one low-molecular-weight organic acid. Despitetheir high dissolution rate, such non-encapsulated granules, having adistribution of ingredients that is substantially homogeneous, have ahigh level of durability in non-ionic surfactants (NIO surfactants).

The present invention accordingly relates to formulations comprising atleast one granulate containing

-   -   a) from 2 to 50% by weight of at least one water-soluble        phthalocyanine compound, based on the total weight of the        granulate,    -   b) from 10 to 60% by weight of at least one anionic dispersing        agent and/or at least one water-soluble organic polymer, based        on the total weight of the granulate,    -   c) from 15 to 75% by weight of at least one inorganic salt        and/or at least one low-molecular-weight organic acid or a salt        thereof, based on the total weight of the granulate,    -   d) from 0 to 10% by weight of at least one further additive,        based on the total weight of the granulate, and    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate.

The sum of the percentages of components a)-e) by weight is always 100%.

The formulation according to the invention may also comprise a mixtureof granulates having different compositions and it is also possible forgranulates not having a composition according to the invention to beused in admixture.

The granulates in the formulations according to the invention are notencapsulated and have a substantially homogeneous distribution ofingredients.

As the phthalocyanine compound for the granulates there come intoconsideration phthalocyanine complexes with di-, tri- or tetra-valentmetals (complexes having a d⁰ or d¹⁰ configuration) as the central atom.

Such complexes are especially water-soluble Zn(II), Fe(II), Ca(II),Mg(II), Na(I), K(I), Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III),Zr(IV), In(III), Sn(IV) and Hf(VI) phthalocyanines, aluminium and zincphthalocyanines being especially preferred.

The granulate of the formulation according to the inventionadvantageously comprises at least one phthalocyanine compound of formula[Me

_(q)

PC

Q₁]_(r) ⁺A_(s) ⁻  (1a)or[Me

_(q)

PC

Q₂]_(r)  (1b)wherein

-   PC is the phthalocyanine ring system;-   Me is Zn; Fe(II); Ca; Mg; Na; K; Al-Z₁; Si(IV); P(V); Ti(IV);    Ge(IV); Cr(VI); Ga(III); Zr(IV); In(III); Sn(IV) or Hf(VI);-   Z₁ is a halide ion, sulfate ion, nitrate ion, acetate ion or hydroxy    ion;-   q is 0, 1 or 2;-   r is from 1 to 4;-   Q₁ is a sulfo or carboxy group; or is a radical of formula    —SO₂X₂—R₆—X₃ ⁺; —O—R₆—X₃ ⁺; or —(CH₂)_(t)—Y₁ ⁺;    wherein-   R₆ is branched or unbranched C₁-C₈alkylene; or 1,3- or    1,4-phenylene;-   X₂ is —NH—; or —N—C₁-C₅alkyl-; X₃ ⁺ is a group of formula    and, in the case where R₆=C₁-C₈alkylene, may also be a group of    formula-   Y₁ ⁺ is a group of formula-   t is 0 or 1;-   in which above formulae,-   R₇ and R₈ are each independently of the other C₁-C₆alkyl;-   R₉ is C₁-C₆alkyl; C₅-C₇cycloalkyl; or NR₁₁R₁₂;-   R₁₀ and R₁₁ are each independently of the other C₁-C₅alkyl;-   R₁₂ and R₁₃ are each independently of the other hydrogen or    C₁-C₅alkyl;-   R₁₄ and R₁₅ are each independently of the other unsubstituted or    hydroxy-, cyano-, carboxy-, C₁-C₆alkoxy-carbonyl-, C₁-C₆alkoxy-,    phenyl-, naphthyl- or pyridyl-substituted C₁-C₆alkyl;-   u is from 1 to 6;-   A₁ is the balance of an aromatic 5- to 7-membered nitrogen    heterocycle which may contain one or two further nitrogen atoms as    ring members, and-   B₁ is the balance of a saturated 5- to 7-membered nitrogen    heterocycle which may contain 1 or 2 further nitrogen, oxygen and/or    sulfur atoms as ring members;-   Q₂ is hydroxy; C₁-C₂₂alkyl; branched C₃-C₂₂alkyl; C₂-C₂₂alkenyl;    branched C₄-C₂₂alkenyl or a mixture thereof; C₁-C₂₂alkoxy; a sulfo    or carboxy radical; a radical of formula    a branched alkoxy radical of formula    an alkylethyleneoxy unit of formula    -(T₁)_(d)—(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of formula COOR₂₃,    wherein-   B₂ is hydrogen; hydroxy; C₁-C₃₀alkyl; C₁-C₃₀alkoxy; —CO₂H; —CH₂COOH;    SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃ ²⁻M₁; —OPO₃ ²⁻M₁; or a mixture thereof;-   B₃ is hydrogen; hydroxy; —COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁; or C₁-C₆alkoxy;-   M₁ is a water-soluble cation;-   T₁ is —O—; or —NH—;-   X₁ and X₄ are each independently of the other —O—; —NH—; or    —N—C₁-C₅alkyl;-   R₁₆ and R₁₇ are each independently of the other hydrogen; a sulfo    group or a salt thereof; a carboxy group or a salt thereof, or a    hydroxy group, at least one of the radicals R₁₆ and R₁₇ being a    sulfo or carboxy group or a salt thereof,-   Y₂ is —O—; —S—; —NH— or —N—C₁-C₅alkyl;-   R₁₈ and R₁₉ are each independently of the other hydrogen;    C₁-C₆alkyl; hydroxy-C₁-C₆alkyl; cyano-C₁-C₆alkyl; sulfo-C₁-C₆alkyl;    carboxy- or halo-C₁-C₆alkyl; unsubstituted or halo-, C₁-C₄alkyl-,    C₁-C₄alkoxy-, sulfo- or carboxy-substituted phenyl; or R₁₈ and R₁₉,    together with the nitrogen atom to which they are bonded, are a    saturated 5- or 6-membered heterocyclic ring which may additionally    contain a further nitrogen or oxygen atom as ring member;-   R₂₀ and R₂₁ are each independently of the other a C₁-C₆alkyl or    aryl-C₁-C₆alkyl radical;-   R₂₂ is hydrogen; or unsubstituted or halo-, hydroxy-, cyano-,    phenyl-, carboxy-, C₁-C₆-alkoxy-carbonyl- or C₁-C₆alkoxy-substituted    C₁-C₆alkyl;-   R₂₃ is C₁-C₂₂alkyl; branched C₄-C₂₂alkyl; C₁-C₂₂alkenyl or branched    C₄-C₂₂alkenyl; C₃-C₂₂-glycol; C₁-C₂₂alkoxy; branched C₄-C₂₂alkoxy;    or a mixture thereof;-   M is hydrogen; or an alkali metal ion or ammonium ion,-   Z₂ ⁻ is a chlorine ion, bromine ion, alkylsulfate ion or    aralkylsulfate ion;-   a is 0 or 1;-   b is from 0 to 6;-   c is from 0 to 100;-   d is 0 or 1;-   e is from 0 to 22;-   v is an integer from 2 to 12;-   w is 0 or 1; and-   A⁻ is an organic or inorganic anion, and-   s in the case of monovalent anions A⁻ is equal to r and in the case    of polyvalent anions is ≦r, it being necessary for A_(s) ⁻ to    balance the positive charge; and when r≠1, the radicals Q₁ may be    identical or different,    and wherein the phthalocyanine ring system may also contain further    solubility-imparting groups.

The number of substituents Q₁ and Q₂ in formula (1a) and in formula(1b), respectively, which substituents may be identical or different, isfrom 1 to 8 and, as is customary with phthalocyanines, the number neednot be a whole number (degree of substitution). If other, non-cationicsubstituents are also present, the sum of the latter and the cationicsubstituents is from 1 to 4. The minimum number of substituents thatneed to be present in the molecule is governed by the water-solubilityof the resulting molecule. An adequate solubility is achieved when theamount of phthalocyanine compound that dissolves is sufficient to causephotodynamically catalysed oxidation on the fibres. A solubility as lowas 0.01 mg/l may be sufficient, but generally a solubility of from 0.001to 1 g/l is expedient.

Halogen is fluorine, bromine or, especially, chlorine.

As groups

there come into consideration especially:

Preference is given to the group

As heterocyclic rings in the group

there likewise come into consideration the groups mentioned above, butwith the bond to the remaining substituents being effected by way of acarbon atom.

In all substituents, phenyl, naphthyl and aromatic hetero rings may besubstituted by one or two further radicals, for example by C₁-C₆alkyl,C₁-C₆alkoxy, halogen, carboxy, C₁-C₆alkoxy-carbonyl, hydroxy, amino,cyano, sulfo, sulfonamido etc.

Preference is given to a substituent from the group C₁-C₆alkyl,C₁-C₆alkoxy, halogen, carboxy, C₁-C₆alkoxy-carbonyl and hydroxy.

As the group

there come into consideration especially:

R₁₁ being as defined above, especially CH₃ or CH₂CH₃.

All above-mentioned nitrogen heterocycles may, in addition, besubstituted by alkyl groups, either at a carbon atom or at a furthernitrogen atom located in the ring, with preference being given to amethyl group as the alkyl group.

A_(s) ⁻ in formula (1a) denotes, as counterion to the positive charge ofthe remainder of the molecule, any desired anion. It is generallyintroduced in the process of manufacture (quaternisation), in which caseit is preferably a halogen ion, an alkylsulfate ion or an arylsulfateion. Among the arylsulfate ions mention should be made of thephenylsulfonate, p-tolysulfonate and p-chlorophenylsulfonate ions. It isalso possible, however, for any other anion to function as the anion,since the anions can readily be interchanged in known manner;accordingly, A_(s) ⁻ may also be a sulfate, sulfite, carbonate,phosphate, nitrate, acetate, oxalate, citrate or lactate ion or anotheranion of an organic carboxylic acid. In the case of monovalent anions,the index s is equal to r. In the case of polyvalent anions, s assumes avalue ≧r but must be such, depending on the conditions, that it exactlybalances the positive charge of the remainder of the molecule.

C₁-C₆Alkyl and C₁-C₆alkoxy are straight-chain or branched alkyl andalkoxy radicals, respectively, for example methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl orhexyl, and methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy or hexyloxy,respectively.

C₂-C₂₂Alkenyl denotes, for example, allyl, methallyl, isopropenyl,2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl,n-dodec-2-enyl or n-octadec-4-enyl.

Preferred phthalocyanine compounds of formula (1a) of the granulatescorrespond to formula

wherein

-   Me, q, PC, X₂, X₃ and R₆ are as defined for formula (1a),-   M is hydrogen; or an alkali metal ion, ammonium ion or amine salt    ion; and the sum of the numbers r₁ and r₂ is from 1 to 4, and-   A_(s) ⁻ exactly balances the positive charge of the remainder of the    molecule, and especially to formula    [Me]_(q)—[Pc]—[SO₂NHR₆′—X₃′⁺A′⁻]_(r),  (3)    wherein-   Me, q and PC are as defined for formula (1a),-   R₆′ is C₂-C₆alkylene;-   r is a number from 1 to 4;-   X₃′ is a group of formula    wherein-   R₇ and R₈ are each independently of the other unsubstituted or    hydroxy-, cyano-, halo- or phenyl-substituted C₁-C₄alkyl;-   R₉ is R₇; cyclohexyl or amino;-   R₁₁ is C₁-C₄alkyl;-   R₂₁, is C₁-C₄alkyl; C₁-C₄alkoxy; halogen; carboxy;    C₁-C₄alkoxy-carbonyl or hydroxy; and-   A′⁻ is a halide ion, alkylsulfate ion or arylsulfate ion;    it being possible for the radicals —SO₂NHR′₆—X₃′⁺A′⁻ to be identical    or different.

Further phthalocyanine compounds that can be used in the granulate ofthe formulations according to the invention correspond to formula[Me

_(q)

PC

SO₃—Y₃′]_(r)  (4)wherein

-   PC is the phthalocyanine ring system;-   Me is Zn; Fe(II); Ca; Mg; Na; K; Al-Z₁; Si(IV); P(V); Ti(IV);    Ge(IV); Cr(VI); Ga(III); Zr(IV); In(III); Sn(IV) or Hf(VI);-   Z₁ is a halide ion, sulfate ion, nitrate ion, acetate ion or hydroxy    ion;-   q is 0; 1; or 2;-   Y₃′ is hydrogen; or an alkali metal ion or ammonium ion; and-   r is any number from 1 to 4.

Of those, very special preference is given to phthalocyanine compoundsof formula (4) wherein

-   Me is Zn or Al-Z₁; and-   Z₁ is a halide ion, sulfate ion, nitrate ion, acetate ion or hydroxy    ion.

Further phthalocyanine compounds of interest that can be used in thegranulate of the formulations according to the invention correspond toformula

wherein

-   PC, Me and q are as defined for formula (4);-   R₁₇′ and R₁₈′ are each independently of the other hydrogen; phenyl;    sulfophenyl; carboxyphenyl; C₁-C₆alkyl; hydroxy-C₁-C₆alkyl;    cyano-C₁-C₆alkyl; sulfo-C₁-C₆alkyl; carboxy-C₁-C₆alkyl or    halo-C₁-C₆alkyl or, together with the nitrogen atom, form a    morpholine ring;-   q′ is an integer from 2 to 6; and-   r is a number from 1 to 4;    it being possible, when r>1, for the radicals    present in the molecule to be identical or different.

Further phthalocyanine compounds of interest that can be used in thegranulate of the formulations according to the invention correspond toformula

wherein

-   PC, Me and q are as defined for formula (4),-   Y′₃ is hydrogen; or an alkali metal ion or ammonium ion,-   q′ is an integer from 2 to 6;-   R₁₇′ and R₁₈′ are each independently of the other hydrogen; phenyl;    sulfophenyl; carboxyphenyl; C₁-C₆alkyl; hydroxy-C₁-C₆alkyl;    cyano-C₁-C₆alkyl; sulfo-C₁-C₆alkyl; carboxy-C₁-C₆alkyl or    halo-C₁-C₆alkyl or, together with the nitrogen atom, form a    morpholine ring,-   m′ is 0 or 1; and-   r and r₁ are each independently of the other any number from 0.5 to    3.5, the sum r+r₁ being a minimum of 1 and a maximum of 4.

Where the central atom Me in the phthalocyanine ring is Si(IV), thephthalocyanines used in the granulate of the formulations according tothe invention may also contain, in addition to the substituents on thephenyl nucleus of the phthalocyanine ring, axial substituents (═R₂₄).

Such phthalocyanines correspond, for example, to formula

wherein

-   R₂₄ is hydroxy; C₁-C₂₂alkyl; branched C₄-C₂₂alkyl; C₁-C₂₂alkenyl;    branched C₄-C₂₂alkenyl or a mixture thereof; C₁-C₂₂alkoxy; a sulfo    or carboxy radical; a radical of formula    a branched alkoxy radical of formula    an alkylethyleneoxy unit of formula    -(T₁)_(d)—(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of formula COOR₂₃    and-   U is [Q₁]_(r) ⁺A_(s) ⁻; or Q₂.

R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃, B₂, B₃, M, Q₁, Q₂, A_(s), T₁,X₁, X₄, Y₂, Z₂ ⁻, a, b, c, d, e, r, v and w therein being as defined forformulae (1a) and (1b).

Especially preferred phthalocyanine compounds are such compounds as arecommercially available and used in washing agent compositions. Usually,the anionic phthalocyanine compounds are in the form of alkali metalsalts, especially sodium salts.

The granulates in the formulations according to the invention containfrom 2 to 50% by weight, preferably from 4 to 30% by weight, especiallyfrom 5 to 20% by weight, of at least one phthalocyanine compound, basedon the total weight of the granulate.

The granulates in the formulations according to the invention containfrom 10 to 60% by weight, preferably from 12 to 60% by weight,especially from 12 to 55% by weight, of at least one anionic dispersingagent and/or at least one water-soluble organic polymer, based on thetotal weight of the granulate.

Such anionic dispersing agents and also the water-soluble organicpolymers, which may also have dispersing properties, are describedhereinbelow.

Anionic Dispersing Agents:

The anionic dispersing agents used are, for example, the commerciallyavailable water-soluble anionic dispersing agents for dyes, pigmentsetc.

The following products, especially, come into consideration:condensation products of aromatic sulfonic acids and formaldehyde,condensation products of aromatic sulfonic acids with unsubstituted orchlorinated biphenyls or biphenyl oxides and optionally formaldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerisedorganic sulfonic acids, sodium salts of polymerisedalkylnaphthalenesulfonic acids, sodium salts of polymerisedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalene-methanesulfonates, ligno- or oxyligno-sulfonates orheterocyclic polysulfonic acids.

Especially suitable anionic dispersing agents are condensation productsof naphthalene-sulfonic acids with formaldehyde sodium salts ofpolymerised organic sulfonic acids,(mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynucleararylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid,lignosulfonates, oxylignosulfonates and condensation products ofnaphthalenesulfonic acid with a polychloromethylbiphenyl.

Instead of or in addition to the dispersing agent or agents, thegranulates according to the invention may comprise a water-solubleorganic polymer, which may also have dispersing properties. Suchpolymers may be used singly or as mixtures of two or more polymers. Aswater-soluble polymers (which may, but need not, have film-formingproperties), there come into consideration, for example, gelatins,polyacrylates, polymethacrylates, copolymers of ethyl acrylate, methylmethacrylate and methacrylic acid (ammonium salt),polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers ofvinylpyrrolidone with long-chain olefins,poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers ofvinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers ofvinyl-pyrrolidone/dimethylaminopropyl acrylamides, quaternisedcopolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates,terpolymers of vinylcaprolactam/vinyl-pyrrolidone/dimethylaminoethylmethacrylates, copolymers of vinylpyrrolidone andmethacrylamidopropyltrimethylammonium chloride, terpolymers ofcaprolactam/vinyl-pyrrolidone/dimethylaminoethyl methacrylates,copolymers of styrene and acrylic acid, polycarboxylic acids,polyacrylamides, carboxymethyl cellulose, hydroxymethyl cellulose,polyvinyl alcohols, hydrolysed and non-hydrolysed polyvinyl acetate,copolymers of maleic acid with unsaturated hydrocarbons and also mixedpolymerisation products of the mentioned polymers. Further suitablesubstances are polyethylene glycol (MW=4000-20 000), copolymers ofethylene oxide with propylene oxide (MW>3500), condensation products(block polymerisation products) of alkylene oxide, especially propyleneoxide, copolymers of vinylpyrrolidone with vinyl acetate, ethyleneoxide-propylene oxide addition products with diamines, especiallyethylenediamine, polystyrenesulfonic acid, polyethylene-sulfonic acid,copolymers of acrylic acid with sulfonated styrenes, gum arabic,hydroxypropyl methylcellulose, sodium carboxymethyl cellulose,hydroxypropyl methylcellulose phthalate, maltodextrin, starch, sucrose,lactose, enzymatically modified and subsequently hydrated sugars, as areobtainable under the name “Isomalt”, cane sugar, polyaspartic acid andtragacanth.

Among those water-soluble organic polymers, special preference is givento carboxymethyl cellulose, polyacrylamides, polyvinyl alcohols,polyvinylpyrrolidones, gelatins, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, maltodextrins,polyaspartic acid and also polyacrylates and polymethacrylates.

The granulates in the formulations according to the invention containfrom 15 to 75% by weight, preferably from 20 to 75% by weight,especially from 25 to 70% by weight, of at least one inorganic saltand/or at least one low-molecular-weight organic acid and/or a saltthereof.

The mentioned components are described in detail hereinbelow:

Inorganic Salts:

For use as inorganic salts there come into consideration carbonates,hydrogen carbonates, phosphates, polyphosphates, sulfates, silicates,sulfites, borates, halides and pyrophosphates, preferably in the form ofalkali metal salts. Preference is given to water-soluble salts such as,for example, alkali metal chlorides, alkali phosphates, alkalicarbonates, alkali polyphosphates and alkali sulfates and water-solublesalts used in washing agent and/or washing agent additive formulations.

Low-Molecular-Weight Organic Acids and Salts Thereof:

There come into consideration as low-molecular-weight acids, forexample, mono- or poly-carboxylic acids. Of special interest arealiphatic carboxylic acids, especially those having a total number offrom 1 to 12 carbon atoms. Preferred acids are aliphatic C₁-C₁₂-mono- or-poly-carboxylic acids, the monocarboxylic acids being especially thosehaving at least 3 carbon atoms in total. As substituents of thecarboxylic acids there come into consideration, for example, hydroxy andamino, especially hydroxy. Special preference is given to aliphaticC₂-C₁₂polycarboxylic acids, especially aliphatic C₂-C₆polycarboxylicacids. Very special preference is given to hydroxy-substituted aliphaticC₂-C₆polycarboxylic acids. These compounds may be used in the form ofthe free acid or a salt, especially an alkali salt.

There may also be used aminopolycarboxylates (e.g. sodiumethylenediaminetetraacetate), phytates, phosphonates,aminopolyphosphonates (e.g. sodium ethylenediaminetetra-phosphonate),aminoalkylenepoly(alkylenephosphonates), polyphosphonates,polycarboxylates or water-soluble polysiloxanes.

As examples of low-molecular-weight organic acids and salts thereofthere may be mentioned oxalic acid, tartaric acid, acetic acid,propionic acid, succinic acid, maleic acid, citric acid, formic acid,gluconic acid, p-toluenesulfonic acid, terephthalic acid, benzoic acid,phthalic acid, acrylic acid and polyacrylic acid.

The granulates in the formulations according to the invention maycomprise further additives, for example wetting agents, disintegrantssuch as, for example, powdered or fibrous cellulose, microcrystallinecellulose, fillers such as, for example, dextrin, water-insoluble orwater-soluble dyes or pigments, and also dissolution accelerators andoptical brighteners. Aluminium silicates such as zeolites, and alsocompounds such as talc, kaolin, TiO₂, SiO₂ or magnesium trisilicate mayalso be used in small amounts. Such additives are present in an amountof from 0 to 10% by weight, preferably from 0 to 5% by weight, based onthe total weight of the granulates.

As especially preferred additives, special emphasis is to be given topowdered or fibrous weight, preferably from 0 to 5% by weight, based onthe total weight of the granulates.

The granulates in the formulations according to the invention maycontain from 3 to 15% water by weight, based on the total weight of thegranulate.

A preferred formulation according to the invention comprises at leastone granulate consisting of

-   -   a) from 4 to 30% by weight of at least one water-soluble        phthalocyanine compound,    -   b) from 12 to 60% by weight of at least one anionic dispersing        agent and/or at least one water-soluble organic polymer,    -   c) from 20 to 75% by weight of at least one inorganic salt        and/or at least one low-molecular-weight organic acid or a salt        thereof,    -   d) from 0 to 5% by weight of at least one further additive, and    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate.

A formulation according to the invention to which greater preference isgiven comprises at least one granulate consisting of

-   -   a) from 5 to 20% by weight of at least one water-soluble        phthalocyanine compound,    -   b) from 12 to 55% by weight of at least one anionic dispersing        agent and/or at least one water-soluble organic polymer,    -   c) from 25 to 70% by weight of at least one inorganic salt        and/or at least one low-i molecular-weight organic acid or a        salt thereof,    -   d) from 0 to 5% by weight of at least one zeolite compound and,        where appropriate, further additives, and    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate.

A likewise preferred formulation according to the invention comprises atleast one granulate consisting of

-   -   a) from 2 to 50% by weight of at least one water-soluble        phthalocyanine compound of formula (2a), (3), (4), (5), (6)        and/or (7) defined above,    -   b) from 10 to 60% by weight of at least one anionic dispersing        agent from the group consisting of condensation products of        naphthalene-sulfonic acid with formaldehyde; sodium salts of        polymerised organic sulfonic acids;        (mono-/di-)alkyl-naphthalenesulfonates; polyalkylated        polynuclear aryl-sulfonates; sodium salts of polymerised        alkylbenzene-sulfonic acids; lignosulfonates; oxylignosulfonates        and condensation products of naphthalenesulfonic acid with a        polychloromethylbiphenyl;        -   and/or at least one water-soluble organic polymer from the            group consisting of carboxymethyl cellulose;            polyacrylamides; polyvinyl alcohols; polyvinylpyrrolidones;            gelatins; hydrolysed polyvinyl acetates; copolymers of            vinylpyrrolidone and vinyl acetate; maltodextrins;            polyaspartic acid; polyacrylates and polymethacrylates, and    -   c) from 15 to 75% by weight of at least one inorganic salt        and/or at least one low-molecular-weight organic acid or a salt        thereof from the group consisting of carbonates; hydrogen        carbonates; phosphates; polyphosphates; sulfates; silicates;        sulfites; borates; halides; pyrophosphates; aliphatic carboxylic        acids having a total number of from 1 to 12 carbon atoms, which        are unsubstituted or substituted by hydroxy and/or by amino;        aminopolycarboxylates; phytates; phosphonates;        aminopolyphosphonates; aminoalkylenepoly(alkylenephosphonates);        polyphosphonates; polycarboxylates; water-soluble polysiloxanes;        and water-soluble salts that are used in washing agent and/or        washing agent additive formulations, and    -   d) from 0 to 10% by weight of at least one further additive from        the group consisting of wetting agents; disintegrants; fillers;        water-insoluble or water-soluble dyes or pigments; dissolution        accelerators; optical brighteners; aluminium silicates; talc;        kaolin; TiO₂, SiO₂; and magnesium trisilicate, and    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate.

The granulates in the formulations according to the invention preferablyhave an average particle size of <500 μm. Greater preference is given tothe particle size of the granulates being from 40 to 400 μm.

The formulations according to the invention can, depending on thecomposition of the granulate according to the invention, be used assuch, as an additive in other formulations or in combination withanother formulation. Preference is given to use of the formulationsaccording to the invention in a washing agent composition or in awashing agent additive, for example, a pre- and/or after-treatmentagent, stain-removing salt, washing-power enhancer, fabric conditioner,bleaching agent or UV-protection enhancer.

The formulations according to the invention are used especially as anadditive in a washing agent formulation. Such a washing agentformulation may be in solid, liquid, gel-like or paste-like form, forexample in the form of a liquid, non-aqueous washing agent compositioncontaining not more than 5% by weight, preferably from 0 to 1% byweight, water and based on a suspension of a builder substance in anon-ionic surfactant, for example as described in GB-A-2 158 454.

The formulations according to the invention may also be in the form ofpowders or (super-)compact powders, in the form of single- ormulti-layer tablets (tabs), in the form of washing agent bars, washingagent blocks, washing agent sheets, washing agent pastes or washingagent gels, or in the form of powders, pastes, gels or liquids used incapsules or in pouches (sachets).

However, the washing agent compositions are preferably in the form ofnon-aqueous formulations, powders, tabs or granules.

The present invention accordingly relates also to washing agentformulations containing

-   I) from 5 to 70% A) of at least one anionic surfactant and/or B) at    least one non-ionic surfactant, based on the total weight of the    washing agent formulation,-   II) from 5 to 60% C) of at least one builder substance, based on the    total weight of the washing agent formulation,-   III) from 0 to 30% D) of at least one peroxide and, optionally, at    least one activator, based on the total weight of the washing agent    formulation, and-   IV) from 0.001 to 1% E) of at least one granulate which contains    -   a) from 2 to 50% by weight of at least one water-soluble        phthalocyanine compound, based on the total weight of the        granulate,    -   b) from 10 to 60% by weight of at least one anionic dispersing        agent and/or at least one, water-soluble organic polymer, based        on the total weight of the granulate,    -   c) from 15 to 75% by weight of at least one inorganic salt        and/or at least one low-molecular-weight organic acid or a salt        thereof, based on the total weight of the granulate,    -   d) from 0 to 10% by weight of at least one further additive,        based on the total weight    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate,-   V) from 0 to 60% F) of at least one further additive, and-   VI) from 0 to 5% G) water.

The sum of the percentages by weight of components I)-VI) in aformulation is always 100%.

All the preferences mentioned hereinbefore apply to the granulate E).

The anionic surfactant A) may be, for example, a sulfate, sulfonate orcarboxylate surfactant or a mixture of those surfactants. Preferredsulfates are those having from 12 to 22 carbon atoms in the alkylradical, where appropriate in combination with alkyl ethoxysulfateshaving from 10 to 20 carbon atoms in the alkyl radical. Preferredsulfonates are, for example, alkylbenzenesulfonates having from 9 to 15carbon atoms in the alkyl radical and/or alkylnaphthalenesulfonateshaving from 6 to 16 carbon atoms in the alkyl radical. The cation in theanionic surfactant is preferably an alkali metal cation, especiallysodium. Preferred carboxylates are alkali metal sarcosinates of theformula R—CO—N(R¹)—CH₂COOM¹, wherein R is alkyl or alkenyl having from 8to 18 carbon atoms in the alkyl or alkenyl radical, R¹ is C₁-C₄alkyl andM¹ is an alkali metal.

The non-ionic surfactant B) may be, for example, a condensation productof from 3 to 8 mols of ethylene oxide with 1 mol of primary alcoholcontaining from 9 to 15 carbon atoms.

There come into consideration as builder substance C), for example,alkali metal phosphates, especially tripolyphosphates, carbonates orhydrogen carbonates, especially the sodium salts, silicates, aluminiumsilicates, polycarboxylates, polycarboxylic acids, organic phosphonates,aminoalkylenepoly(alkylenephosphonates) or mixtures of those compounds.Especially suitable silicates are sodium salts of crystalline silicateshaving layered structures of the formula NaHSi_(t)O_(2t+1).pH₂O orNa₂Si_(t)O_(2t+1).pH₂O, wherein t is a number from 1.9 to 4 and p is anumber from 0 to 20. Among the aluminium silicates, preference is givento those obtainable commercially under the names zeolite A, B, X and HS,and also to mixtures comprising two or more of those components.

Among the polycarboxylates, preference is given topolyhydroxycarboxylates, especially citrates, and acrylates and alsocopolymers thereof with maleic anhydride. Preferred polycarboxylic acidsare nitrilotriacetic acid, ethylenediaminetetraacetic acid andethylenediamine disuccinate either in racemic form or in theenantiomerically pure S,S form. Phosphonates andaminoalkylenepoly(alkylenephosphonates) that are especially suitable arealkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid,nitrilotris(methylenephosphonic acid),ethylenediaminetetramethylenephosphonic acid anddiethylenetriamine-pentamethylenephosphonic acid.

There come into consideration as the peroxide component D), for example,the organic and inorganic peroxides known in the literature andavailable commercially that bleach textile materials at conventionalwashing temperatures, for example at from 10 to 95° C. The organicperoxides are, for example, mono- or poly-peroxides, especially organicperacids or salts thereof, such as phthalimidoperoxycaproic acid,peroxybenzoic acid, diperoxydodecanoic diacid, diperoxynonanoic diacid,diperoxydecanoic diacid, diperoxyphthalic acid or salts thereof.Preferably, however, inorganic peroxides are used, such as, for example,persulfates, perborates, percarbonates and/or persilicates. It will beunderstood that mixtures of inorganic and/or organic peroxides can alsobe used. The peroxides may be in a variety of crystalline forms and havedifferent water contents, and they may also be used together with otherinorganic or organic compounds in order to improve their storagestability. The peroxides are added to the washing agent compositionpreferably by mixing the components, for example using a screw meteringsystem and/or a fluidised bed mixer.

The washing agent compositions may comprise, in addition to thecombination according to the invention, one or more optical brighteners,for example from the class bis-triazinylaminostilbenedisulfonic acid,bis-triazolylstilbenedisulfonic acid, bis-styrylbiphenyl andbis-benzofuranylbiphenyl, a bis-benzoxalyl derivative,bis-benzimidazolyl derivative, coumarin derivative or a pyrazolinederivative.

The washing agent compositions may also comprise suspending agents fordirt, e.g. sodium carboxymethyl cellulose, pH regulators, e.g. alkalimetal or alkaline earth metal silicates, foam regulators, e.g. soap,salts for regulating the spray-drying and the granulating properties,e.g. sodium sulfate, fragrances and, optionally, antistatic agents andfabric conditioners, enzymes, such as amylase, bleaching agents,pigments and/or toning agents. It will be understood that suchconstituents must be stable towards the bleaching agent used.

Further preferred additives to the washing agent compositions accordingto the invention are polymers which, during the washing of textiles,prevent staining caused by dyes in the washing liquor which have beenreleased from the textiles under the washing conditions. Such polymersare preferable polyvinylpyrrolidones which, where appropriate, have beenmodified by the incorporation of anionic or cationic substituents,especially those polyvinylpyrrolidones having a molecular weight in therange from 5000 to 60 000, more especially from 10 000 to 50 000. Suchpolymers are preferably used in an amount of from 0.05 to 5% by weight,especially from 0.2 to 1.7% by weight, based on the total weight of thewashing agent composition.

In addition, the washing agent compositions according to the inventionmay also comprise so-called perborate activators, such as, for example,TAED or TAGU. Preference is given to TAED, which is preferably used inan amount of from 0.05 to 5% by weight, especially from 0.2 to 1.7% byweight, based on the total weight of the washing agent composition.

The percentages of components I) to VI) in the washing agentformulations hereinbelow are in all cases based on the total weight ofthe washing agent formulation.

A preferred washing agent formulation according to the inventionconsists of

-   I) from 5 to 70% A) of at least one anionic surfactant from the    group consisting of alkylbenzenesulfonates having from 9 to 15    carbon atoms in the alkyl radical; alkyl-naphthalenesulfonates    having from 6 to 16 carbon atoms in the alkyl radical; and alkali    metal sarcosinates of the formula R—CO—N(R₁)—CH₂COOM₁,    -   wherein R is alkyl or alkenyl having from 8 to 18 carbon atoms        in the alkyl or alkenyl radical,    -   R₁ is C₁-C₄alkyl and    -   M₁ is an alkali metal and/or    -   B) at least one non-ionic surfactant from the group consisting        of condensation products of from 3 to 8 mols of ethylene oxide        with 1 mol of primary alcohol containing from 9 to 15 carbon        atoms,-   II) from 5 to 60% C) of a builder substance from the group    consisting of alkali metal phosphates; carbonates; hydrogen    carbonates; silicates; aluminium silicates; polycarboxylates;    poly-carboxylic acids; organic phosphonates and    amino-alkylenepoly(alkylenephosphonates), and-   III) from 0 to 30% D) of a peroxide from the group consisting of    organic mono- or poly-peroxides; organic peracids and salts thereof;    persulfates; perborates; percarbonates and persilicates,-   IV) from 0.001 to 1% E) of a granulate which contains    -   a) from 2 to 50% by weight of at least one water-soluble        phthalocyanine compound of formula (2a), (3), (4), (5), (6)        and/or (7) defined above,    -   b) from 10 to 60% by weight of at least one anionic dispersing        agent from the group consisting of condensation products of        naphthalene-sulfonic acid with formaldehyde; sodium salts of        polymerised organic sulfonic acids;        (mono-/di-)alkylnaphthalenesulfonates; polyalkylated polynuclear        arylsulfonates; sodium salts of polymerised alkylbenzenesulfonic        acids; lignosulfonates; oxylignosulfonates and condensation        products of naphthalenesulfonic acid with a        polychloromethylbiphenyl;        -   and/or at least one water-soluble organic polymer from the            group consisting of carboxymethyl cellulose;            polyacrylamides; polyvinyl alcohols; polyvinylpyrrolidones;            gelatins; hydrolysed polyvinyl acetates; copolymers of            vinylpyrrolidone and vinyl acetate; maltodextrins;            polyaspartic acid; polyacrylates and polymethacrylates, and    -   c) from 15 to 75% by weight of at least one inorganic salt        and/or at least one low-molecular-weight organic acid or a salt        thereof from the group consisting of carbonates; hydrogen        carbonates; phosphates; polyphosphates; sulfates; silicates;        sulfites; borates; halides; pyrophosphates; aliphatic carboxylic        acids having a total number of from 1 to 12 carbon atoms, which        are unsubstituted or substituted by hydroxy and/or by amino;        aminopolycarboxylates; phytates; phosphonates;        aminopolyphosphonates; aminoalkylenepoly-(alkylenephosphonates);        polyphosphonates; polycarboxylates; water-soluble polysiloxanes;        and water-soluble salts used in washing agent and/or washing        agent additive formulations, and    -   d) from 0 to 10% by weight of at least one further additive from        the group consisting of wetting agents; disintegrants; fillers;        water-insoluble or water-soluble dyes or pigments; dissolution        accelerators; optical brighteners; aluminium silicates; talc;        kaolin; TiO₂, SiO₂; and magnesium trisilicate, and    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate,-   V) from 0 to 60% F) of further additives from the group consisting    of optical brighteners; suspending agents for dirt; pH regulators;    foam regulators; salts for regulating the spray-drying and    granulating properties; fragrances; antistatic agents; fabric    conditioners; enzymes; bleaching agents; pigments; toning agents;    polymers which, during the washing of textiles, prevent staining    caused by dyes in the washing liquor which have been released from    the textiles under the washing conditions; and perborate activators,    and-   VI) from 0 to 5% G) water.

The granulates E) are prepared, for example, in the following manner:

Firstly, an aqueous solution of the phthalocyanine compound is prepared,to which there is added at least one dispersing agent and/or at leastone polymer and at least one inorganic salt and/or at least onelow-molecular-weight organic acid or a salt thereof and, whereappropriate, further additives; stirring is carried out, whereappropriate with heating, until a homogeneous solution (or a dilutesuspension if water-insoluble additives are used) is obtained. Thesolids content of the solution obtained should preferably be at least15% by weight, especially from 20 to 45% by weight, based on the totalweight of the mixture. The viscosity of the solution is preferably below600 mPas. The phthalocyanine is preferably present in the slurry in thedissolved state.

The aqueous solution (or suspension) of the phthalocyanine compound isthen subjected to a drying step in which all water, with the exceptionof a residual amount, is removed, solid particles (granules)simultaneously being formed. Known methods are suitable for producingthe granulates from the aqueous solution. In principle, both continuousmethods and drying and fluidised bed granulation processes.

Especially suitable are spray-drying processes in which the activeingredient solution is sprayed into a chamber with circulating hot air.The atomisation of the solution is carried out using single or binarynozzles or is brought about by the spinning effect of a rapidly rotatingdisc. In order to increase the particle size, the spray-drying processmay be combined with additional agglomeration of the liquid particleswith solid nuclei in a fluidised bed that forms an integral part of thechamber (so-called fluidised spray). The fine particles (<100 μm)obtained by a conventional spray-drying process may, if necessary afterbeing separated from the exhaust gas flow, be fed as nuclei, withoutbeing further treated, directly into the spray cone of the atomiser ofthe spray-dryer, for the purpose of agglomeration with the liquiddroplets of the active ingredient. During the granulation step, thewater can be rapidly removed from the solutions comprisingphthalocyanine compound, dispersing agent and/or organic polymer, saltand, where appropriate, further additives, and it is expressly intendedthat agglomeration of the droplets forming in the spray cone, i.e. theagglomeration of droplets with solid particles, will take place.Preference is given to the use of agglomeration processes to produce thegranulates according to the invention because such processes usuallyyield a higher bulk weight so that the granulates have bettercompatibility with washing agent formulations.

A further embodiment of the present invention comprises using, forpreparation of the granulates, phthalocyanine solutions that have beenpurified by membrane separation procedures.

If necessary the granules formed in the spray-dryer are removed in acontinuous process, for example by a sieving operation. The fines andthe oversize particles are either recycled directly to the process(without being redissolved) or are dissolved in the liquid activeingredient formulation and subsequently granulated again.

The residual water content of the granulates E) may be from 3 to 15% byweight.

The granulates are resistant to abrasion, low in dust, free-flowing andcan be readily metered. They are distinguished especially by very rapidsolubility in water.

The granulates E) preferably have a density in the range from 500 to 900g/l, dissolve rapidly in water and do not float on the surface of thewashing agent solution. They may be added in the desired concentrationof the phthalocyanine compound directly to the washing agentformulation.

The content of granulates E) in accordance with the invention in theformulations according to the invention is from to 0.001 to 1% byweight, preferably from 0.001 to 0.05% by weight and very especiallyfrom 0.005 to 0.03% by weight.

The washing agent formulation according to the invention can be preparedin a generally known manner.

A formulation in powder form can be prepared, for example, by firstpreparing an initial powder by spray-drying an aqueous slurry comprisingall of the afore-mentioned components except for components D) and E)and then adding the dry components D) and E) and mixing all of themtogether. It is also possible to start from an aqueous slurry which,although comprising components A) and C), does not comprise component B)or comprises only a portion of component B). The slurry is spray-dried;component E) is then mixed with component B) and added; and thencomponent D) is mixed in dry. The components are preferably mixed withone another in such amounts that a solid compact washing agentcomposition in granule form is obtained, having a specific weight of atleast 500 g/l.

In another preferred embodiment, the production of the washing agentcomposition is carried out in three steps. In the first step a mixtureof anionic surfactant (and, where appropriate, a small amount ofnon-ionic surfactant) and builder substance is prepared. In the secondstep that mixture is sprayed with the major portion of the non-ionicsurfactant and then, in the third step, peroxide and, where appropriate,catalyst, and the granulate according to the invention are added. Thatmethod is usually carried out in a fluidised bed. In a further preferredembodiment, the individual steps are not carried out completelyseparately, so that there is a certain amount of overlap between them.Such a method is usually carried out in an extruder, in order to obtaingranulates in the form of “megapearls”.

As an alternative thereto, the granulates according to the inventioncan, for the purpose of admixture with a washing agent in a post-dosingstep, be mixed with other washing agent components such as phosphates,zeolites, brighteners or enzymes.

A mixture of that kind for post-dosing of the granulates isdistinguished by a homogeneous distribution of the granulates accordingto the invention in the mixture and can consist of, for example, from 5to 50% granulates and from 95 to 50% sodium tripolyphosphate. Where thedark appearance of the granulate in the washing agent composition is tobe suppressed, this can be achieved, for example, by embedding thegranules in droplets of a whitish meltable substance (“water-solublewax”) or, preferably, by encapsulating the granules in a melt consistingof, for example, a water-soluble wax, as described in EP-B-0 323 407 B1,a white solid (e.g. titanium dioxide) being added to the melt in orderto reinforce the masking effect of the capsule.

A further aspect of the present invention relates to novel granulates E)which contain

-   -   a) from 2 to 50% by weight of at least one water-soluble        phthalocyanine compound, based on the total weight of the        granulate,    -   b) from 10 to 60% by weight of at least one anionic dispersing        agent and/or at least one water-soluble organic polymer, based        on the total weight of the granulate,    -   c) from 15 to 75% by weight of at least one inorganic salt        and/or at least one low-molecular-weight organic acid or a salt        thereof, based on the total weight of the granulate,    -   d) from 0 to 10% by weight of at least one further additive,        based on the total weight of the granulate, and    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate,        with the proviso that they do not contain ethoxylated        stearyidiphenyloxyethyldiethyltriamine.

All the preferences mentioned hereinbefore apply to the novel granulatesE) according to the invention.

A further aspect of the present invention relates to novel preferredgranulates E) which contain

-   -   a) from 4 to 30% by weight of at least one water-soluble        phthalocyanine compound,    -   b) from 12 to 60% by weight of at least one anionic dispersing        agent and/or at least    -   c) from 20 to 75% by weight of at least one inorganic salt        and/or at least one low-molecular-weight organic acid or a salt        thereof,    -   d) from 0 to 5% by weight of at least one further additive, and    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate,        with the proviso that they do not contain ethoxylated        stearyldiphenyloxyethyldiethyltriamine.

A further aspect of the present invention relates to novel, moreespecially preferred, granulates E) which contain

-   -   a) from 5 to 20% by weight of at least one water-soluble        phthalocyanine compound,    -   b) from 12 to 55% by weight of at least one anionic dispersing        agent and/or at least one water-soluble organic polymer,    -   c) from 25 to 70% by weight of at least one inorganic salt        and/or at least one low-molecular-weight organic acid or a salt        thereof,    -   d) from 0 to 5% by weight of at least one zeolite compound and,        where appropriate, further additives, and    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate,        with the proviso that they do not contain ethoxylated        stearyidiphenyloxyethyldiethyltriamine.

A further aspect of the present invention relates to novel, likewisemore especially preferred, granulates E) which contain

-   -   a) from 2 to 50% by weight of at least one water-soluble        phthalocyanine compound of formula (2a), (3), (4), (5), (6)        and/or (7) defined above, and    -   b) from 10 to 60% by weight of at least one anionic dispersing        agent from the group consisting of condensation products of        naphthalene-sulfonic acid with formaldehyde; sodium salts of        polymerised organic sulfonic acids;        (mono-/di-)alkylnaphthalenesulfonates; polyalkylated polynuclear        arylsulfonates; sodium salts of polymerised alkylbenzenesulfonic        acids; lignosulfonates; oxylignosulfonates and condensation        products of naphthalenesulfonic acid with a        polychloromethylbiphenyl;        -   and/or at least one water-soluble organic polymer from the            group consisting of carboxymethyl cellulose;            polyacrylamides; polyvinyl alcohols; polyvinylpyrrolidones;            gelatins; hydrolysed polyvinyl acetates; copolymers of            polyaspartic acid; polyacrylates and polymethacrylates, and    -   c) from 15 to 75% by weight of at least one inorganic salt        and/or at least one low-molecular-weight organic acid or a salt        thereof from the group consisting of carbonates; hydrogen        carbonates; phosphates; polyphosphates; sulfates; silicates;        sulfites; borates; halides; pyrophosphates; aliphatic carboxylic        acids having a total number of from 1 to 12 carbon atoms, which        are unsubstituted or substituted by hydroxy and/or by amino;        aminopolycarboxylates; phytates; phosphonates;        aminopolyphosphonates; aminoalkylenepoly-(alkylenephosphonates);        polyphosphonates; polycarboxylates, water-soluble polysiloxanes,        and water-soluble salts used in washing agent and/or washing        agent additive formulations, and    -   d) from 0 to 10% by weight of at least one further additive from        the group consisting of wetting agents; disintegrants; fillers;        water-insoluble or water-soluble dyes or pigments; dissolution        accelerators; optical brighteners; aluminium silicates; talc;        kaolin; TiO₂; SiO₂; and magnesium trisilicate, and    -   e) from 3 to 15% by weight water, based on the total weight of        the granulate,        with the proviso that they do not contain ethoxylated        stearyldiphenyloxyethyldiethyltriamine.

Preferred granulates are as defined hereinbefore, with the proviso thatthey are not encapsulated and have a substantially homogeneousdistribution of ingredients.

All the preferences described hereinbefore for the granulate E) in thewashing agent formulation according to the invention apply toconstituents a) to e) of the novel granulate according to the invention.

The following Examples serve to illustrate the invention, withoutlimiting the invention thereto. For that purpose, on the one hand,compositions and the preparation of solutions comprising thephthalocyanine compounds are described and, on the other hand, it isdescribed how, using different technologies, those solutions are furtherprocessed in order to prepare the granulates according to the invention.Unless otherwise specified, parts and percentages are based on weight.Temperatures are, unless otherwise specified, in degrees Celsius.

Composition of, and Preparation of, Solutions of PhthalocyanineCompounds:

EXAMPLE 1

564 g of an aqueous solution of an aluminium phthalocyanine compound,which solution has been purified of organic by-products by membraneseparation procedures and has a solids content of 19.5% by weight, areintroduced into a glass beaker. To that solution there are added 1857 gof an aqueous solution containing 541 g of an anionic dispersing agent(condensation product of naphthalenesulfonic acid and formaldehyde) and270 g of sodium sulfate. The aqueous solution is homogenised by stirringat 25° C. for 1 hour. A solution having a solids content of 38% isobtained, the proportions in the dissolved material being 12% by weightof the phthalocyanine compound, 59% by weight of the dispersingagent/polymer and 29% by weight of the salt.

EXAMPLES 2-11

The following solutions of phthalocyanine compounds are prepared by thesame method. The phthalocyanine solutions used were purified of organicby-products by membrane separation procedures. Where a zeolite orcellulose are used as additives, they can be suspended in the aqueoussolution of phthalocyanine compound, dispersing agent/polymer and salt.Table 1 gives the solids content and the percentage proportions of therespective components in the dissolved solids. TABLE 1 Examples 2-11Example 2 3 4 5 6 7 8 9 10 11 a) Phthalocyanine compound Aluminiumphthalocyanine 11 10 5 3 5 8 11 7 Zinc phthalocyanine 12 8 2.4 12 10 810 3 b) Dispersing agent/polymer Sodium salt of polymerised 25alkylnaphthalenesulfonic acid Condensation product of formaldehyde 13 5216 39 with naphthalenesulfonic acid Oxylignosulfonate, sodium saltAlkylnaphthalenesulfonic acid, sodium salt 31 Dinaphthylmethanesulfonicacid, sodium salt Sodium lignosulfonate 23 31 Methylene-linkedcondensation product of 9 2 17 13 12 51 arylsulfonic acids andhydroxyarylsulfonic acids Maltodextrin 14 4 6 c) Salt/acid Sodiumsulfate 49 45 30 32 36 71 61 45 39 Sodium carbonate 11 Sodium citrate 3018 Sodium phosphate 12 8 Polyphosphate, sodium salt 13 1 6 Sodiumchloride 9 d) Additives Fibrous cellulose 0.6 Solids content of thesolutions (% by weight) 28 24 30 33 32 31 23 25 27 33

EXAMPLE 12

560 g of an aqueous solution of a zinc phthalocyanine compound, whichsolution has been purified of organic by-products by membrane separationprocedures and has a solids content of 12.5% by weight, are introducedinto a glass beaker and heated to 40° C. A solution of 160 g of a drypulverulent anionic dispersing agent (condensation product offormaldehyde with naphthalenesulfonic acid) and 50 g of a maltodextrin1613 g of water is added to the heated solution. Then 300 g of sodiumsulfate, 160 g of sodium citrate and 100 g of sodium tripolyphosphateare added in portions to the solution and finally 200 g of a previouslyprepared aqueous polyaspartic acid solution (solids content: 20% byweight) are added. The solution obtained has a solids content of 28% andis stirred further at 40° C. until the solids have completely dissolved.The proportions of the phthalocyanine compound, dispersing agent/polymerand salts are 8% by weight, 28% by weight and 64% by weight,respectively.

EXAMPLES 13 to 22

Solutions having the following compositions are prepared by the samemethod as in Example 12. The phthalocyanine solutions used were purifiedof organic by-products by membrane separation procedures. Where azeolite or cellulose are used as additives, they can be suspended in theaqueous solution of phthalocyanine compound, dispersing agent/polymerand salt. Table 2 below gives the percentage proportions (% by weight)of the respective components in the solids content. TABLE 2 Examples13-22 Example 13 14 15 16 17 18 19 20 21 22 a) Phthalocyanine compoundAluminium phthalocyanine 11 6 4 13 5 6 4 5 2 Zinc phthalocyanine 10 3 1415 6 5 4.2 9 b) Dispersing agent/polymer Sodium salt of polymerised 16alkylnaphthalenesulfonic acid Condensation product of formaldehyde with50 14 27 50 naphthalenesulfonic acid Oxylignosulfonate, sodium salt 16Alkylnaphthalenesulfonic acid, sodium salt 12 7.4 Sodium lignosulfonate23 Dinaphthylmethanesulfonic acid, sodium salt 1 5 Methylene-linkedcondensation product of 25 14 10 8.8 30 arylsulfonic acids andhydroxyarylsulfonic acids Maltodextrin 9 10 11 Polyaspartic acid 12 2 4Polyvinyl alcohol 3 Vinylpyrrolidone/vinyl acetate copolymer 1Carboxymethyl cellulose 2 Polyacrylate 3 Polyacrylamide 1 Gelatin 2 c)Salt/acid Sodium sulfate 18 37 70 36 35 74 19 15 29 45 Sodium citrate 616 16 20 5.5 Sodium phosphate 4 8 Polyphosphate, sodium salt 1 8 10 4Sodium chloride 3 10 15 d) Additives Zeolite 3 1.1 Solids content of thesolutions (% by weight) 35 32 22 24 25 23 30 24 28 26

EXAMPLES 23-70

Preparation of Granulates from the Solutions of Examples 1 to 22

Preparation of the granulates is carried out, as mentioned already, byremoving all water, except for the residual moisture, from the solutionsprepared above, by means of a drying step. Merely by simply drying thesolutions in a vacuum cabinet and comminuting the resulting solid in amixer, followed by sieving, particles having very good dissolutioncharacteristics can be obtained. Preferred granulation methods consistof drying and simultaneous granulation in a spray-dryer, a disc tower, abench fluidised spray-dryer or in a fluidised bed granulator. TheExamples that follow illustrate the invention, without limiting itthereto.

EXAMPLE 23

The solution prepared in Example 1, consisting of phthalocyaninecompound, salt and dispersing agent, is spray-dried in a spray-dryerequipped with a single nozzle. The inlet air temperature is 190° C. withan exhaust air temperature of 105° C. The product obtained is afree-flowing granulate having an average particle size of 70 μm and abulk density of 520 g/l with a residual water content of 6% by weight.The granulate thereby prepared contains 11% by weight aluminiumphthalocyanine compound, 56% by weight dispersing agent and 27% byweight salt.

EXAMPLES 24-33

Using the same method as in Example 23, granulates are prepared fromsome of the solutions described in Examples 2 to 22 by spray-drying, thecompositions of the granulates being given in Table 3. The granulatesare free-flowing with an average particle diameter in the range 50-80 μmand have a bulk density of 500-550 g/l. TABLE 3 Examples 24-33 Solutiona) Phthalocyanine, b) Disp./pol., c) Salt/acid, d) Additive, Water, Ex.from Ex. % by weight % by weight % by weight % by weight % by weight 242 10 25 58 — 7 25 5 7 55 32 1 5 26 6 14 48 30 — 8 27 8 15 12 65 — 8 2810 10 37 49 — 4 29 11 9 47 36 — 8 30 13 20 48 26 — 6 31 17 12 24 57 — 732 19 6 53 34 — 7 33 21 9 55 27 3 6

EXAMPLE 34

Preparation of the granulates is carried out by spray-drying thesolutions described in Examples 1 to 22. In contrast to the method ofExamples 23 to 33, the fines produced during the drying process arecontinuously separated off from the exhaust air stream and passeddirectly into the spray cone of the nozzle tower by means of a gasstream. The granulates thereby produced are much coarser and also denserthan those of Examples 22 to 33 and have a much reduced fines content(less than 5% of particles below 20 μm). The average particle size is110 μm with a bulk density of 540-580 g/l.

EXAMPLE 35

The solution prepared in Example 3, consisting of phthalocyaninecompound, polymer, salt and dispersing agent, is spray-dried in a dryingtower equipped with a disc atomiser. The inlet air temperature is 205°C. with an exhaust air temperature of 102° C. The product obtained is afree-flowing granulate having an average particle size of 65 μm and abulk density of 510 g/l with a residual water content of 7% by weight.The granulate thereby prepared contains 12% by weight dispersingagent/polymer, 70% by weight salt and 11% by weight zinc phthalocyaninecompound.

EXAMPLES 36-43

Using the same method as in Example 35, granulates are prepared fromsome of the solutions described in Examples 1 to 22 by spray-drying in adisc tower. The granulates are free-flowing with an average particlediameter of 70 μm and have a bulk density of 520-540 g/l. Theircompositions are given in Table 4. TABLE 4 Examples 36-43 Solution a)Phthalocyanine, b) Disp./pol., c) Salt/acid, d) Additive, Water, Ex.from Ex. % by weight % by weight % by weight % by weight % by weight 365 7 53 31 1 8 37 7 14 22 58 — 6 38 8 15 13 68 — 4 39 9 10 26 57 — 7 4014 8 46 38 — 8 41 15 17 12 67 — 4 42 17 12 25 58 — 5 43 22 10 35 48 1 6

EXAMPLE 44

The solution prepared in Example 11 is granulated in a bench fluidisedspray-dryer. In the first phase of the granulation process, nuclei arebuilt up in the fluidised bed (inlet air temperature 200° C., bedtemperature 95° C.). Once sufficient nuclei have been built up in thebed, the bed temperature is lowered to about 48° C. in order to initiategranulation. Granulation of the entire solution is carried out in arange for the bed temperature of from 47 to 50° C. The granulateobtained has a residual moisture content of 9% at the outlet from thegranulator and is subsequently dried in a continuously operating fluidbed with warm air to a desired value of 6%. The product obtained is afree-flowing granulate having an average particle size of 130 μm and abulk density of 610 g/l, with proportions of 9% by weight phthalocyaninecompound, 48% by weight dispersing agent/polymer and 37% by weight saltin the solid material.

EXAMPLES 45-57

Using the same method as in Example 44, granulates are prepared fromsolutions of Examples 1 to 22 by granulating in a bench fluidisedspray-dryer and, where appropriate, subsequently drying in acontinuously operated fluid bed. The granulates obtained arefree-flowing with an average particle diameter of around 120-150 μm and,depending on the composition of the active-ingredient-containingsolution and the granulation parameters, have a bulk density of 500-800g/l. The compositions of the granulates are listed in Table 5. TABLE 5Examples 45-57 Solution a) Phthalocyanine, b) Disp./pol., c) Salt/acid,d) Additive, Water, Ex. from Ex. % by weight % by weight % by weight %by weight % by weight 45 1 11 54 27 — 8 46 2 10 24 55 — 11 47 4 17 48 30— 5 48 5 7 53 31 1 8 49 6 14 49 31 — 6 50 9 10.5 27 58 — 4.5 51 12 7 2660 — 7 52 13 19 47 26 — 8 53 14 8 46 38 — 8 54 16 14 23 55 — 8 55 18 1114 70 — 5 56 20 9 35 51 — 5 57 21 9 55 27 3 6

EXAMPLE 58

A portion of the solution prepared in Example 22, consisting ofphthalocyanine compound, salt, dispersing agent and zeolite, is dried invacuo for 24 hours and the solid obtained is comminuted in a laboratorymixer. The product obtained is transferred to a laboratory fluidised bedgranulator. (STREA-1, Aeromatic AG, Bubendorf, Switzerland) asgranulating nuclei and fluidised by means of warm air (about 65° C.)flowing in through the perforated tray. The solution of Example 6 iscontinuously sprayed into that fluidised bed using a binary nozzle.After about 120 minutes and after the introduction of about 4000 g ofsolution, granulation is terminated by stopping the introduction ofsolution. The granulates obtained are dried in the same apparatus, usingwarm air at 80° C., to a residual moisture content of 8% by weight.After discharging the product, the fines are removed from the granulateby sieving. A free-flowing granulate is obtained having an averageparticle size of 310 μm and a bulk density of 680 g/l. The proportionsin the solid material are 10% by weight for the phthalocyaninecompounds, 34% by weight for the dispersing agents, 47% by weight forthe salts and 1% by weight for the zeolite.

EXAMPLES 59-70

Using the same method as in Example 58, granulates are prepared fromsolutions of Examples 1 to 21. These granulates are free-flowing with anaverage particle diameter of around 220-350 μm and have a bulk densityof 600-750 g/l. The compositions of the granulates are given in Table 6.TABLE 6 Examples 5-970 Solution a) Phthalocyanine, b) Disp./pol., c)Salt/acid, d) Additive, Water, Ex. from Ex. % by weight % by weight % byweight % by weight % by weight 59 1 11 55 27 — 7 60 3 11 12 68 — 9 61 417 47 30 — 6 62 5 7 53 31 1 8 63 6 14 48 31 — 7 64 9 10 26 56 — 8 65 109 35 45 — 11 66 12 7 25 56 — 12 67 13 20 48 26 — 6 68 14 9 48 39 — 4 6919 6 52 34 — 8 70 21 9 55 27 3 6Washing Agent Preparations Comprising the Granulates According to theInvention

Examples 71 to 88 illustrate the use of the granulates according to theinvention in washing agent preparations, without limiting it thereto.TABLE 7 Examples 71-80 Examples 71 72 73 74 75 76 77 78 79 80Constituents (% by weight) A) Sodium salt of lauryl benzenesulfonic acid10 10 10 10 10 10 10 10 10 10 Sodium lauryl ether sulfate (AES) 3 3 3 33 3 3 3 3 3 B) Neodol 23-6.5E (alcohol ethoxylate) 4 4 4 4 4 4 4 4 4 4C) Zeolite A (sodium aluminium silicate) 25 20 22 35 10 25 32 25 Sodiumtripolyphosphate 10 30 35 5 32 D) Sodium percarbonate 20 20 20 5 20Sodium perborate 20 20 20 NOBS (p-nonanoyl-oxybenzenesulfonate) 3 3 3 E)Granulates, Ex. 23-70 0.03 0.01 0.01 0.02 0.02 0.005 0.02 0.005 0.010.02 F) Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Cellulase 1.51.5 1.5 1.5 Protease 1.5 1.5 1.5 1.5 1.5 1.5 Polycarboxylate 4 4 4 4 4 4Carboxymethyl cellulose 2 2 2 2 2 2 2 2 2 2 Sodium sulfate 15 13 18 2522 20 9 25 8 10 Sodium carbonate 10 7 10 7 7 5 13 8 6 TAED(tetraacetyl-ethylenediamine) 3 3 3 1 3

Further additives in small amounts (foam inhibitors etc.) and theresidual moisture content of the washing agent formulation make thecomposition up to 100%. TABLE 8 Examples 81-88 Examples 81 82 83 84 8586 87 88 Sodium salt of lauryl benzenesulfonic acid 8% 8% 8% 8% 8% 8% 8%8% Sodium lauryl ether sulfate (AES) 3% 3% 3% 3% 3% 3% 3% 3% Neodol23-6.5E (non-ionic alcohol ethoxylate) 5% 5% 5% 5% 5% 5% 5% 5% Zeolite A20%  20%  20%  20%  20%  20%  20%  20%  Polycarboxylate (co-builder) 5%5% 5% 5% 5% 5% 5% 5% Sodium carbonate 18%  18%  18%  18%  18%  18%  18% 18%  Sodium silicate 4% 4% 4% 4% 4% 4% 4% 4% Sodium sulfate 5% 5% 5% 5%5% 5% 5% 5% Hydroxyethanediphosphonic acid (complexer) 0.5%   0.5%  0.5%   0.5%   0.5%   0.5%   0.5%   0.5%   Cellulase 1.5%   1.5%   1.5%  1.5%   1.5%   1.5%   Protease 1.5%   1.5%   Carboxymethyl cellulose 1%1% 1% 1% 1% 1% 1% 1% Sodium perborate monohydrate 15%  15%  15%  15% 15%  15%  15%  15%  TAED 5% 5% 5% 5% 5% 5% 5% 5% Soap 2% 2% 2% 2% 2% 2%2% 2% Granulate E) 0.03 0.005 0.02 0.008 0.01 0.03 0.02 0.02Further additives in small amounts and the residual moisture content ofthe washing agent formulation make the composition up to 100%.

1. A formulation comprising at least one granulate containing a) from 2to 50% by weight of at least one water-soluble phthalocyanine compound,based on the total weight of the granulate, b) from 10 to 60% by weightof at least one anionic dispersing agent and/or at least onewater-soluble organic polymer, based on the total weight of thegranulate, c) from 15 to 75% by weight of at least one inorganic saltand/or at least one low-molecular-weight organic acid or a salt thereof,based on the total weight of the granulate, d) from 0 to 10% by weightof at least one further additive, based on the total weight of thegranulate, and e) from 3 to 15% by weight water, based on the totalweight of the granulate.
 2. A formulation according to claim 1, whereinthe granulate comprises, as phthalocyanine compound, at least onewater-soluble Zn(II), Fe(II), Ca(II), Mg(II), Na(I), K(I), Al, Si(IV),P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI)phthalocyanine compound.
 3. A formulation according to claim 1, whereinthe granulate comprises at least one phthalocyanine compound of formula[Me

_(q)

PC

Q₁]_(r) ⁺A_(s) ⁻  (1a)or[Me

_(q)

PC

Q₂]_(r)  (1b) wherein PC is the phthalocyanine ring system; Me is Zn;Fe(II); Ca; Mg; Na; K; Al-Z₁; Si(IV); P(V); Ti(IV); Ge(IV); Cr(VI);Ga(III); Zr(IV); In(III); Sn(IV) or Hf(VI); Z₁ is a halide ion, sulfateion, nitrate ion, acetate ion or hydroxy ion; q is 0, 1 or 2; r is from1 to 4; Q₁ is a sulfo or carboxy group; or is a radical of formula—SO₂X₂—R₆—X₃ ⁺; —O—R₆—X₃ ⁺; or —(CH₂)_(t)—Y₁ ⁺; wherein R₆ is branchedor unbranched C₁-C₈alkylene; or 1,3- or 1,4-phenylene; X₂ is —NH—; or—N—C₁-C₅alkyl-; X₃ ⁺ is a group of formula

and, in the case where R₆=C₁-C₈alkylene, may also be a group of formula

Y₁ ⁺ is a group of formula

t is 0 or 1; in which above formulae, R₇ and R₈ are each independentlyof the other C₁-C₆alkyl; R₉ is C₁-C₆alkyl; C₅-C₇cycloalkyl; or NR₁₁R₁₂;R₁₀ and R₁₁ are each independently of the other C₁-C₅alkyl; R₁₂ and R₁₃are each independently of the other hydrogen or C₁-C₅alkyl; R₁₄ and R₁₅are each independently of the other unsubstituted or hydroxy-, cyano-,carboxy-, C₁-C₆alkoxy-carbonyl-, C₁-C₆alkoxy-, phenyl-, naphthyl- orpyridyl-substituted C₁-C₆alkyl; u is from 1 to 6; A₁ is the balance ofan aromatic 5- to 7-membered nitrogen heterocycle which may contain oneor two further nitrogen atoms as ring members, and B₁ is the balance ofa saturated 5- to 7-membered nitrogen heterocycle which may contain 1 or2 further nitrogen, oxygen and/or sulfur atoms as ring members; Q₂ ishydroxy; C₁-C₂₂alkyl; branched C₃-C₂₂alkyl; C₂-C₂₂alkenyl; branchedC₄-C₂₂alkenyl or a mixture thereof; C₁-C₂₂alkoxy; a sulfo or carboxyradical; a radical of formula

a branched alkoxy radical of formula

an alkylethyleneoxy unit of formula -(T₁)_(d)—(CH₂)_(b)(OCH₂CH₂)_(a)—B₃or an ester of formula COOR₂₃, wherein B₂ is hydrogen; hydroxy;C₁-C₃₀alkyl; C₁-C₃₀alkoxy; —CO₂H; —CH₂COOH; SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃²⁻M₁; —OPO₃ ²⁻M₁; or a mixture thereof; B₃ is hydrogen; hydroxy; —COOH;—SO₃ ⁻M₁; —OSO₃ ⁻M₁; or C₁-C₆alkoxy; M₁ is a water-soluble cation; T₁ is—O—; or —NH—; X₁ and X₄ are each independently of the other —O—; —NH—;or —N—C₁-C₅alkyl; R₁₆ and R₁₇ are each independently of the otherhydrogen; a sulfo group or a salt thereof; a carboxy group or a saltthereof, or a hydroxy group, at least one of the radicals R₁₆ and R₁₇being a sulfo or carboxy group or a salt thereof, Y₂ is —O—; —S—; —NH—or —N—C₁-C₅alkyl; R₁₈ and R₁₉ are each independently of the otherhydrogen; C₁-C₆alkyl; hydroxy-C₁-C₆alkyl; cyano-C₁-C₆alkyl;sulfo-C₁-C₆alkyl; carboxy- or halo-C₁-C₆alkyl; unsubstituted or halo-,C₁-C₄alkyl-, C₁-C₄alkoxy-, sulfo- or carboxy-substituted phenyl; or R₁₈and R₁₉, together with the nitrogen atom to which they are bonded, are asaturated 5- or 6-membered heterocyclic ring which may additionallycontain a further nitrogen or oxygen atom as ring member; R₂₀ and R₂₁are each independently of the other a C₁-C₆alkyl or aryl-C₁-C₆alkylradical; R₂₂ is hydrogen; or unsubstituted or halo-, hydroxy-, cyano-,phenyl-, carboxy-, C₁-C₆alkoxy-carbonyl- or C₁-C₆alkoxy-substitutedC₁-C₆alkyl; R₂₃ is C₁-C₂₂alkyl; branched C₄-C₂₂alkyl; C₁-C₂₂alkenyl orbranched C₄-C₂₂alkenyl; C₃-C₂₂glycol; C₁-C₂₂alkoxy; branchedC₄-C₂₂alkoxy; or a mixture thereof; M is hydrogen; or an alkali metalion or ammonium ion, Z₂ ⁻ is a chlorine ion, bromine ion, alkylsulfateion or aralkylsulfate ion; a is 0 or 1; b is from 0 to 6; c is from 0 to100; d is 0 or 1; e is from 0 to 22; v is an integer from 2 to 12; w is0 or 1; and A⁻ is an organic or inorganic anion, and s in the case ofmonovalent anions A⁻ is equal to r and in the case of polyvalent anionsis ≧r, it being necessary for A_(s) ⁻ to balance the positive charge;and when r≠1, the radicals Q₁ may be identical or different, and whereinthe phthalocyanine ring system may also contain furthersolubility-imparting groups.
 4. A formulation according to claim 3,wherein the granulate comprises at least one phthalocyanine compound offormula

wherein Me, q, PC, X₂, X₃ and R₆ are as defined for formula (1a), M ishydrogen; or an alkali metal ion, ammonium ion or amine salt ion; andthe sum of the numbers r₁ and r₂ is from 1 to 4, and A_(s) ⁻ exactlybalances the positive charge of the remainder of the molecule, or offormula[Me]_(q)—[PC

SO₂NHR₆′X₃′⁺A′⁻]_(r),  (3) wherein Me, q and PC are as defined forformula (1a), R₆′ is C₂-C₆alkylene; r is a number from 1 to 4; X₃′ is agroup of formula

wherein R₇ and R₈ are each independently of the other unsubstituted orhydroxy-, cyano-, halo- or phenyl-substituted C₁-C₄alkyl; R₉ is R₇;cyclohexyl or amino; R₁₁ is C₁-C₄alkyl; R₂₁ is C₁-C₄alkyl; C₁-C₄alkoxy;halogen; carboxy; C₁-C₄alkoxy-carbonyl or hydroxy; and A′⁻ is a halideion, alkylsulfate ion or arylsulfate ion; it being possible for theradicals —SO₂NHR′₆—X₃′⁺A⁻ to be identical or different.
 5. A formulationaccording to claim 3, wherein the granulate comprises at least onephthalocyanine compound of formula[Me

_(q)

PC

SO₃—Y₃′]_(r)  (4) wherein PC is the phthalocyanine ring system; Me isZn; Fe(II); Ca; Mg; Na; K; Al-Z₁; Si(IV); P(V); Ti(IV); Ge(IV); Cr(VI);Ga(III); Zr(IV); In(III); Sn(IV) or Hf(VI); Z₁ is a halide ion, sulfateion, nitrate ion, acetate ion or hydroxy ion; q is 0; 1; or 2; Y₃′ ishydrogen; or an alkali metal ion or ammonium ion; and r is any numberfrom 1 to
 4. 6. A formulation according to claim 5, wherein thegranulate comprises at least one phthalocyanine compound of formula (4)wherein Me is Zn or Al-Z₁; and Z₁ is a halide ion, sulfate ion, nitrateion, acetate ion or hydroxy ion.
 7. A formulation according to claim 3,wherein the granulate comprises at least one phthalocyanine compound offormula

wherein PC, Me and q are as defined for formula (4); R₁₇′ and R₁₈′ areeach independently of the other hydrogen; phenyl; sulfophenyl;carboxyphenyl; C₁-C₆alkyl; hydroxy-C₁-C₆alkyl; cyano-C₁-C₆alkyl;sulfo-C₁-C₆alkyl; carboxy-C₁-C₆alkyl or halo-C₁-C₆alkyl or, togetherwith the nitrogen atom, form a morpholine ring; q′ is an integer from 2to 6; and r is a number from 1 to 4; it being possible, when r>1, forthe radicals

present in the molecule to be R₁₈′ identical or different.
 8. Aformulation according to claim 3, wherein the granulate comprises atleast one phthalocyanine compound of formula

wherein PC, Me and q are as defined for formula (4), Y′₃ is hydrogen; oran alkali metal ion or ammonium ion, q′ is an integer from 2 to 6; R₁₇′and R₁₈′ are each independently of the other hydrogen; phenyl;sulfophenyl; carboxyphenyl; C₁-C₆alkyl; hydroxy-C₁-C₆alkyl;cyano-C₁-C₆alkyl; sulfo-C₁-C₆alkyl; carboxy-C₁-C₆alkyl orhalo-C₁-C₆alkyl or, together with the nitrogen atom, form a morpholinering, m′ is 0 or 1; and r and r₁ are each independently of the other anynumber from 0.5 to 3.5, the sum r+r₁ being a minimum of 1 and a maximumof
 4. 9. A formulation according to claim 3, wherein the granulatecomprises at least one phthalocyanine compound of formula

wherein R₂₄ is hydroxy; C₁-C₂₂alkyl; branched C₄-C₂₂alkyl;C₁-C₂₂alkenyl; branched C₄-C₂₂alkenyl or a mixture thereof;C₁-C₂₂alkoxy; a sulfo or carboxy radical; a radical of formula

a branched alkoxy radical of formula

an alkylethyleneoxy unit of formula -(T₁)_(d)—(CH₂)_(b)(OCH₂CH₂)_(a)—B₃or an ester of formula COOR₂₃; and U is [Q₁]_(r) ⁺A_(s) ⁻; or Q₂; R₁₆,R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂, R₂₃, B₂, B₃, M, Q₁, Q₂, A_(s), T₁, X₁, X₄,Y₂, Z₂ ⁻, a, b, c, d, e, r, v and w therein being as defined forformulae (1a) and (1b). 10-13. (canceled)
 14. A formulation according toclaim 1, wherein the granulate comprises, as anionic dispersing agent,one or more condensation products selected from the group consisting of:condensation products of aromatic sulfonic acids and formaldehyde,condensation products of aromatic sulfonic acids with unsubstituted orchlorinated biphenyls or biphenyl oxides and optionally formaldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerisedorganic sulfonic acids, sodium salts of polymerisedalkylnaphthalenesulfonic acids, sodium salts of polymerisedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalenemethanesulfonates, ligno- or oxyligno-sulfonates andheterocyclic polysulfonic acids.
 15. (canceled)
 16. A formulationaccording to claim 1, wherein the granulate comprises, as water-soluble(but not necessarily film-forming) polymer, one or more compoundsselected from the group consisting of: gelatins, polyacrylates,polymethacrylates, copolymers of ethyl acrylate, methyl methacrylate andmethacrylic acid (ammonium salt), polyvinylpyrrolidones,vinylpyrrolidones, vinyl acetates, copolymers of vinylpyrrolidone withlong-chain olefins, poly(vinylpyrrolidone/dimethylaminoethylmethacrylates), copolymers of vinylpyrrolidone/dimethylaminopropylmethacrylamides, copolymers of vinylpyrrolidone/dimethylaminopropylacrylamides, quaternised copolymers of vinylpyrrolidones anddimethylaminoethyl methacrylates, terpolymers ofinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of vinylpyrrolidone and methacrylamidopropyltrimethylammoniumchloride, terpolymers of caprolactam/vinylpyrrolidone/dimethylaminoethylmethacrylates, copolymers of styrene and acrylic acid, polycarboxylicacids, polyacrylamides, carboxymethyl cellulose, hydroxymethylcellulose, polyvinyl alcohols, hydrolysed and non-hydrolysed polyvinylacetate, copolymers of maleic acid with unsaturated hydrocarbons andalso mixed polymerisation products of the mentioned polymers,polyethylene glycol (MW=4000-20 000), copolymers of ethylene oxide withpropylene oxide (MW>3500), condensation products (block polymerisationproducts) of alkylene oxides,—copolymers of vinylpyrrolidone with vinylacetate, ethylene oxide-propylene oxide addition products with diamines,polystyrenesulfonic acid, polyethylenesulfonic acid, copolymers ofacrylic acid with sulfonated styrenes, gum arabic, hydroxypropylmethylcellulose, sodium carboxymethyl cellulose, hydroxypropylmethylcellulose phthalate, maltodextrin, starch, sucrose, lactose,enzymatically modified and subsequently hydrated sugars, polyasparticacid and tragacanth. 17-19. (canceled)
 20. A formulation according toclaim 1, wherein the granulate comprises, as inorganic salt and/orlow-molecular-weight organic acid and/or a salt thereof, at least onecompound selected from the group consisting of carbonates; hydrogencarbonates; phosphates; polyphosphates; sulfates; silicates; sulfites;borates; halides; pyrophosphates; aliphatic carboxylic acids having atotal number of from 1 to 12 carbon atoms, which are unsubstituted orsubstituted by hydroxy and/or by amino; aminopolycarboxylates; phytates;phosphonates; aminopolyphosphonates;aminoalkylenepoly(alkylenephosphonates); polyphosphonates;polycarboxylates; water-soluble polysiloxanes; and a water-soluble saltsused in washing agent and/or washing agent additive formulations. 21.(canceled)
 22. A formulation according to claim 20, wherein thegranulate comprises, as low-molecular-weight organic acid, oxalic acid,tartaric acid, acetic acid, propionic acid, succinic acid, maleic acid,citric acid, formic acid, gluconic acid, p-toluenesulfonic acid,terephthalic acid, benzoic acid, phthalic acid, acrylic acid and/orpolyacrylic acid and/or a salt thereof.
 23. (canceled)
 24. A formulationaccording to claim 1, wherein the granulate further comprises from 0 to5% by weight of a wetting agent, a disintegrant, a filler, awater-insoluble or water-soluble dye or pigment, and/or a dissolutionaccelerator, an optical brightener, a zeolite, talc, powdered cellulose,fibrous cellulose, microcrystalline cellulose, kaolin, TiO₂, SiO₂ and/ormagnesium trisilicate.
 25. A formulation according to claim 1, whereinthe granulate consists of a) from 4 to 30% by weight of at least onewater-soluble phthalocyanine compound, b) from 12 to 60% by weight of atleast one anionic dispersing agent and/or at least one water-solubleorganic polymer, c) from 20 to 75% by weight of at least one inorganicsalt and/or at least one low-molecular-weight organic acid or a saltthereof, d) from 0 to 5% by weight at least one further additive, and e)from 3 to 15% by weight water, based on the total weight of thegranulate. 26-27. (canceled)
 28. A formulation according to claim 1,wherein the granulate has an average particle size of <500 μm. 29.(canceled)
 30. A washing agent composition, washing agent additive oradditive concentrate which comprises a formulation according to claim 1.31. A composition according to claim 30, which is a component of a pre-and/or after-treatment agent, stain-removing salt, washing-powerenhancer, fabric conditioner, bleaching agent and/or UV-protectionenhancer.
 32. (canceled)
 33. A washing agent formulation consisting ofI) from 5 to 70% A) of at least one anionic surfactant and/or B) atleast one non-ionic surfactant, based on the total weight of the washingagent formulation, II) from 5 to 60% C) of at least one buildersubstance, based on the total weight of the washing agent formulation,III) from 0 to 30% D) of at least one peroxide and, optionally, at leastone activator, based on the total weight of the washing agentformulation, and IV) from 0.001 to 1% E) of at least one granulate asdefined in claim 1, and V) from 0 to 60% F) of at least one furtheradditive, and VI) from 0 to 5% G) water.
 34. (canceled)
 35. A processfor the preparation of a granulate according to claim 1, wherein firstlyan aqueous solution of the phthalocyanine compound is prepared, to whichthere is added the anionic dispersing agent and/or the polymer or apolymer solution, the salt and, where appropriate, further additives,and stirring is carried out until a homogeneous solution (or suspension)is obtained, and then all the water, with the exception of a residualamount, is removed from the aqueous solution in a drying step, solidparticles (granules) simultaneously being formed. 36-39. (canceled) 40.A process according to claim 35, wherein the phthalocyanine solution ispurified of organic by-products by a membrane separation procedure. 41.A granulate as defined in claim 1 with the proviso that it does notcontain ethoxylated stearyidiphenyloxyethyldiethyltriamine.
 42. Agranulate as defined in claim 41 with the proviso that it is notencapsulated and it has a substantially homogeneous distribution ofingredients.
 43. A method of treating textiles which comprisescontacting them with a formulation according to claim 1.